CN1828802A - Electron emission source, its method of fabrication, an electron emission device using the electron emission source - Google Patents
Electron emission source, its method of fabrication, an electron emission device using the electron emission source Download PDFInfo
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- CN1828802A CN1828802A CNA2006100588998A CN200610058899A CN1828802A CN 1828802 A CN1828802 A CN 1828802A CN A2006100588998 A CNA2006100588998 A CN A2006100588998A CN 200610058899 A CN200610058899 A CN 200610058899A CN 1828802 A CN1828802 A CN 1828802A
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- emission source
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/04—Cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2329/00—Electron emission display panels, e.g. field emission display panels
- H01J2329/02—Electrodes other than control electrodes
- H01J2329/04—Cathode electrodes
- H01J2329/0407—Field emission cathodes
- H01J2329/0439—Field emission cathodes characterised by the emitter material
- H01J2329/0444—Carbon types
- H01J2329/0455—Carbon nanotubes (CNTs)
Abstract
An electron emission source-forming composition includes a carbon-based material; a vehicle composed of a resin component and a solvent component; and at least one element chosen from (a) at least one metal oxide with an average particle diameter in a range of from 100 to 1,000 nm selected from Al 2 O 3 , TiO 2 , and SiO 2 , and (b) a lead (Pb) free frit. The electron emission source-forming composition is sintered under an air atmosphere during electron emission source formation. Therefore, carbon deposits after sintering and degradation of Carbon Nano-Tubes (CNTs) upon sintering can be remarkably reduced. As a result, the electron emission source formed using the composition has a high current density and the electron emission device using the electron emission source exhibits enhanced reliability.
Description
Require preference
The application with reference to, in conjunction with and follow 35 U.S.C § 119 and require the application early submitting to and distributed series number No.10-2005-0017180 in good time in Korea S Department of Intellectual Property on March 2nd, 2005, the ownership equity of " AN ELECTRON EMISSION SOURCE; APREPARING METHOD THEREOF, AND AN ELECTRONEMISSION DEVICE USING THE SAME ".
Technical field
The electron emission device that the present invention relates to electron emission source, its preparation method and adopt this electron emission source.Particularly, the present invention relates to alleviate carbon-based material at electron emission source, its preparation method of the degeneration (degradation) of sintering process and the electron emission device that adopts this electron emission source.
Background technology
Electron emission device is this display: under the electric field that when having applied voltage on anode and the negative electrode, produces, and the fluorescent material in the phosphor powder layer of cathode electronics emission source electrons emitted collision positive plate, luminous generation image.
Carbon-based material, comprise the carbon nano-tube (CNT) with good electrical electronic conductivity, the advantage that has is such as good electrical conductivity and improved effect (field enhancement effect), low work content, good field emission characteristic, low driving voltage and fabricate devices on large tracts of land.So, estimate that carbon-based material is the desirable electron emission source of electron emission device.
Can contain pasting (paste) method CNT, that form the composition of the electron emission source CNT that on substrate, grows and prepare the electron emission source of CNT base by adopting chemical vapor deposition (CVD) for example or adopting to utilize.With regard to coating method, advantage is that electron emission source can prepare with low cost on large tracts of land.For example, in U.S. Patent No. 6436221, discussed and contained composition CNT, that form electron emission source.
Adopt the conventional electrical emission source preparation method of carbon-based material to relate to sintered composition to form electron emission source.Sintering process carries out in inert gas atmosphere, in case because carbon-based material causes the electronics emission to be degenerated such as the thermal decomposition of CNT.
But sintering can not guarantee fully to have removed the organic material that is used to prepare this electron emission source etc. in inert gas atmosphere, thereby causes electron emissivity to be degenerated.Particularly, when adopting flint glass material component in the preparation at electron emission source, the thermal decomposition of CNT just takes place.Therefore, along with electron emission device preparation technology's carrying out, the electronics emission is degenerated may be more serious.
Summary of the invention
The invention provides the preparation electron emission source composition, use said composition electron emission source, prepare the method for this electron emission source and by adopting this electron emission source to improve the electron emission device of reliability, wherein said composition sintering and alleviated carbon-based material in sintering process in air atmosphere is such as the degeneration of carbon nano-tube (CNT).
According to an aspect of the present invention, provide electron emission source, it comprises: carbon-based material; With at least a average particulate diameter be 100-1000nm, be selected from Al
2O
3, TiO
2And SiO
2Metal oxide.Based on the carbon-based material of 1 weight portion, the content of this metal oxide is the 5-100 weight portion.
Electron emission source preferably also comprises, based on 1 weight portion carbon-based material, and unleaded (Pb) frit of 0.25-10 weight portion.Unit's lead glass material is tin oxide-phosphorus pentoxide (SnO-P preferably
2O
5).
According to a further aspect in the invention, provide electron emission source, it comprises: carbon-based material; And lead-less glasses material.Lead-less glasses material is SnO-P
2O
5Based on the carbon-based material of 1 weight portion, lead-less glasses material content is the 0.25-10 weight portion preferably.
According to another aspect of the invention, provide electron emission source, it comprises: first substrate that is configured to face one another and second substrate; The negative electrode that on first substrate, forms; With the electron emission source that the cathodic electricity that forms on first substrate is connected, it comprises carbon-based material and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm; The anode that on second substrate, forms; With cause luminous fluorescence coating by the electron emission source electrons emitted.
According to a further aspect in the invention, provide electron emission source, it comprises: first substrate that is configured to face one another and second substrate; The negative electrode that on first substrate, forms; With the electron emission source that the cathodic electricity that forms on first substrate is connected, it comprises carbon-based material and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm, and wherein based on the carbon-based material of 1 weight portion, metal oxide content is the 5-100 weight portion; The anode that on second substrate, forms; With cause luminous fluorescence coating by the electron emission source electrons emitted.
According to a further aspect in the invention, provide electron emission source, it comprises: first substrate that is configured to face one another and second substrate; The negative electrode that on first substrate, forms; With the electron emission source that the cathodic electricity that forms is connected, comprise carbon-based material and Pb frit on first substrate; The anode that on second substrate, forms; With cause luminous fluorescence coating by the electron emission source electrons emitted.
According to a further aspect in the invention, provide electron emission source, having comprised: first substrate that is configured to face one another and second substrate; The negative electrode that on first substrate, forms; With the electron emission source that the cathodic electricity that forms on first substrate is connected, comprise carbon-based material and Pb frit, wherein based on the carbon-based material of 1 weight portion, the content of lead-less glasses material is the 0.25-10 weight portion; The anode that on second substrate, forms; With cause luminous fluorescence coating by the electron emission source electrons emitted.
According to a further aspect in the invention, provide the composition that forms electron emission source, it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With at least a Al that is selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm.Based on the carbon-based material of 1 weight portion, the content of described metal oxide is preferably the 5-100 weight portion.The particle diameter of metal oxide preferably makes that through adjusting the difference of particle diameter (D90) of the particle diameter (D10) of 10 weight % particle size distribution and 90 weight % particle size distribution is 300nm or lower.
Based on the carbon-based material of 1 weight portion, said composition preferably also comprises the Pb frit of 0.25-10 weight portion.Described lead-less glasses material is SnO-P preferably
2O
5
According to a further aspect in the invention, provide the composition that forms electron emission source, it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With no Pb frit.Described lead-less glasses material is SnO-P preferably
2O
5Based on the carbon-based material of 1 weight portion, lead-less glasses material content is the 0.25-10 weight portion preferably.
According to a further aspect in the invention, provide the method that forms electron emission source, this method comprises: preparation forms the composition of electron emission source, and it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With at least a Al that is selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm; The composition of this formation electron emission source of printing on substrate; With in oxygen gas atmosphere or contain in the atmosphere of mist of oxygen and nitrogen the composition that sintering is printed.
According to a further aspect in the invention, provide the method that forms electron emission source, this method comprises: preparation forms the composition of electron emission source, and it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With no Pb frit; The composition of this formation electron emission source of printing on substrate; With in oxygen gas atmosphere or contain in the atmosphere of mist of oxygen and nitrogen the composition that sintering is printed.
The composition of this formation electron emission source preferably also comprises at least a component that is selected from photoresist resin, light trigger and filler; The composition that prints this formation electron emission source preferably includes: with the composition coated substrate of this formation electron emission source; Expose with electron emission source area and develop according to substrate.
The sintering of this printing composition preferably carries out 350 ℃-500 ℃ temperature.
Description of drawings
When with reference to below detailed description and consider in conjunction with the accompanying drawings and more in depth understand when of the present invention, to become apparent understanding more fully of the present invention and many attendant advantages of the present invention, identical in the accompanying drawings Reference numeral is represented same or analogous part, wherein:
Fig. 1 is the constructed profile of electron emission device according to embodiments of the present invention; With
Fig. 2-the 4th is used to prepare and forms the present invention and prepare embodiment 1 and 3 and the Al of the composition of the electron emission source of comparative preparation embodiment 1
2O
3, lead-less glasses material and flint glass material differential thermal analysis (DTA) figure.
Embodiment
Below with reference to the accompanying drawing that has wherein provided exemplary of the present invention, invention has been carried out describing more fully.
The invention provides the composition that forms electron emission source, it comprises carbon-based material, carrier and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm.The composition of this formation electron emission source may further include unleaded (Pb) frit.This lead-less glasses material can be tin oxide-phosphorus pentoxide (SnO-P
2O
5), but be not limited thereto.
As mentioned above, the average particulate diameter of the preferred metal oxide that uses in this article is 100-1000nm.If the average particulate diameter of this metal oxide is less than 100nm, metal oxide particle is difficult to disperse so.On the other hand, if surpass 1000nm, then be difficult to emitting electrons and injected hole.
Difference between the particle diameter (D90) of the particle diameter (D10) of the particle of this metal oxide 10 weight % and the particle of 90 weight % is 300nm or lower, especially 10-300nm.If the difference of D10 and D90 surpasses 300nm, can bring out arc discharge in the emission so on the scene.
Preferably, the average particulate diameter of metal oxide is 100-1000nm, and the smallest particles diameter (Dmin) and the largest particles diameter (Dmax) of this metal oxide are respectively 10nm-1300nm simultaneously.If the smallest particles diameter (Dmin) of metal oxide then is difficult to prepare slurry less than 10nm.On the other hand, if the largest particles diameter (Dmax) of metal oxide surpasses 1300nm, then be difficult to emitting electrons and injected hole, and may bring out arc discharge.
Based on the carbon-based material of 1 weight portion, the content of metal oxide is the 5-100 weight portion preferably, is more preferably the 10-60 weight portion.
Metal oxide forms existence in the composition of electron emission source at this, make can be in air atmosphere sintering, thereby effectively prevented this carbon-based material, such as the degeneration of CNT.
It is basic by carbon-based material, carrier with there is not the composition that forms electron emission source that the Pb frit is formed that the present invention also provides.
In this aspect of the invention, based on the carbon-based material of 1 weight portion, the content of no Pb frit is the 0.25-10 weight portion preferably.Be not lower than 0.25 weight portion if there is the content of Pb frit, the adhesiveness of electron emission source descends so.On the other hand, if surpass 10 weight portions, then electron emission matter reduces.
The carbon-based material that the present invention adopts has excellent conductivity and electron emission matter, is used for operating the fluorescent material of the fluorescence coating emitting electrons of the pole plate that faces south with the fluorescence excitation layer at electron emission device.The non-limiting example of carbon-based material comprises carbon nano-tube, graphite, diamond, fullerene and carborundum.Carbon nano-tube most preferably.
Contained carrier is in order to the impressionability and the viscosity of the composition of regulating this formation electron emission source in the composition of formation electron emission source of the present invention.This carrier is made of resin Composition and solvent composition.Resin Composition is preferably at least a to be selected from celluosic resin (such as ethyl cellulose and NC Nitroncellulose), acrylic resin (such as polyester acrylate, epoxy acrylate and urethane acrylate) and vinyl (such as polyvinyl acetate, polyvinyl butyral resin and polyvinylether), but is not limited thereto.In these resin Compositions some also can be served as the photoresist resin.
Solvent compositions preferably is selected from least a of terpinol, butyl carbitol (BC), acetate of butyl carbitol (BCA), toluene and texanol.Preferred terpinol.
Based on the carbon-based material of 1 weight portion, the content of resin Composition is the 1-5 weight portion preferably, is more preferably the 2-3 weight portion.
Based on the carbon-based material of 1 weight portion, solvent composition content is the 5-15 weight portion preferably, preferred 8-12 weight portion.If the resin Composition of formation carrier and the content of solvent composition beyond above-mentioned scope, then should form the impressionability and the mobile decline of the composition of electron emission source.Particularly, if the content of the resin Composition of formation carrier and solvent composition surpasses 15 weight portions, then can seriously hinder drying.
When needing, the composition of formation electron emission source of the present invention can also comprise at least a component that is selected from photoresist resin, light trigger and filler.
The photoresist that can use in the present invention is the material that is used for patterning electronics emission source.The unrestricted example of photoresist resin comprises acrylate-based monomer, benzophenone based monomer, acetophenone base monomer and thioxanthene ketone group monomer.Particularly, the photoresist resin can be epoxy acrylate, polyester acrylate, 2, and 4-diethyl oxanthrone (2,4-diethyloxanthone) or 2,2-dimethoxy-2-phenyl acetophenone.Based on the carbon-based material of 1 weight portion, photoresist content can be the 3-10 weight portion, preferred 5-8 weight portion.If photoresist content is lower than 3 weight portions, the sensitivity of then exposing descends.On the contrary, if surpass 10 weight portions, it is relatively poor then to develop.
Light trigger is used for causing the cross-linking reaction of photoresist resin when exposure.Light trigger can be a benzophenone, but is not limited thereto.Based on the carbon-based material of 1 weight portion, photoinitiator levels can be the 3-10 weight portion, preferred 5-8 weight portion.If photoinitiator levels is lower than 3 weight portions, then make the patterning difficulty owing to cross-linking reaction efficient is low.On the contrary, if surpass 10 weight portions, then production cost increases.
Filler is to be used to improve the conductivity of adhering to inadequate nano inorganic material on substrate.Filler can be Ag or Au, but is not limited thereto.
To describe the method that the composition that adopts above-mentioned formation electron emission source forms electron emission source below in detail.
At first, prepare the composition that forms electron emission source according to said components and its content.This composition that forms electron emission source as mentioned above, so omitted detailed description to it.
Next, the composition with this formation electron emission source is printed on the substrate.Term used herein " substrate " is meant the substrate that is used to form electron emission source.Substrate type can become according to required electron emission source device, and this is in those skilled in the art's ken.For example, when preparation comprised the electron emission device of the gate electrode between negative electrode and anode, substrate can be a negative electrode.When preparation comprised the electron emission device of the gate electrode that is positioned at the negative electrode downside, substrate can be the insulating barrier that makes this negative electrode and grid electrode insulating.
Whether the operation of printing the composition of this formation electron emission source exists according to the photoresist resin and difference.When the composition that forms electron emission source comprises the photoresist resin, do not require independent photoresist patterning.That is to say, the composition of this formation electron emission source is coated on the substrate, expose according to required electron emission source area subsequently and develop.
On the other hand, when not comprising the photoresist resin in the composition of this formation electron emission source, require wherein to have adopted the photoetching process of independent photoresist patterning.That is to say that photoresist film is formed on the substrate and patterning forms the photoresist pattern, formed the composition of this formation electron emission source of printing on the substrate of this photoresist pattern then in the above.
The composition of the formation electron emission source of printing is at oxygen atmosphere or contain 1000ppm or oxygen still less, sintering in the nitrogen atmosphere of concrete 10-500ppm oxygen.By sintering in oxygen atmosphere, the carbon-based material that is included in the composition of this formation electron emission source effectively adheres on the substrate, by the evaporative removal carrier, other material is melted such as inorganic bond and solidifies subsequently, thereby improves the durability of electron emission source.
According to the evaporating temperature and the time of contained carrier in the composition that forms electron emission source at this, determine sintering temperature.Usually, sintering temperature is at 350-500 ℃, preferred 450 ℃.If sintering temperature is lower than 350 ℃, then carrier for evaporating is insufficient.On the other hand, if surpass 500 ℃, then manufacturing cost increases, and substrate may be destroyed.
When needing, the sintered products of gained can be activated.Activation can be undertaken by following: with can for example containing the surface conditioning agent of polyimides by being heated and cured into the solution of film, apply the sintered products of gained, heat subsequently and peel off by adding the film of thermosetting.Replacedly, activation also can be by forming the viscosity part on the cylinder surface that is driven by drive source, and suppresses the sintered products of gained with this cylinder and carry out under predetermined pressure.By activation, the inorganic material of nano-scale can be exposed on the surface of electron emission source or vertical arrangement is embarked on journey.
The electron emission source that forms according to said method comprises carbon-based material and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm.In some cases, electron emission source can also comprise no Pb frit.
Electron emission source of the present invention can also be made up of carbon-based material and no Pb frit substantially.
According to the present invention, by sintering in the presence of oxygen, the carbon containing organic compound in forming the composition of electron emission source is by more effectively thermal decomposition, makes the carbon content that deposits in electron emission source behind the sintering significantly reduce.
The current density of this electron emission source of the present invention is 400-1100 μ A/cm when 5V/ μ m
2, be more preferably 600-1100 μ A/cm
2Electron emission source with this current density is applicable to display device or as the electron emission device of back light unit.
Fig. 1 shows and comprises the example of the electron emission device of electron emission source as mentioned above.
Fig. 1 is the electron emission device figure that has audion according to an embodiment of the present invention.Referring to Fig. 1, electron emission device 200 comprises upper plate 201 and lower plate 202.Upper plate 201 comprises upper substrate 190, be arranged on the anode 180 on the lower surface 190a of upper substrate 190 and be arranged on fluorescence coating 170 on the lower surface 180a of anode 180.
Lower plate 202 comprises lower substrate 110, and described lower substrate 110 and upper substrate 190 are parallel and separate to limit the inner space; Be arranged on negative electrode 120 on the lower substrate 110 with the bar paten form; With the bar paten form gate electrode 140 to intersect with negative electrode 120 is set; Be arranged on the insulating barrier 130 between gate electrode 140 and the negative electrode 120; The electronics launch hole that limits by insulating barrier 130 and gate electrode 140; In electronics launch hole 169, be arranged to aspect ratio gate electrode 140 electron emission sources 160 low and that be electrically connected with negative electrode 120.Therefore electron emission source 160 has omitted detailed description as mentioned above.
Upper plate 201 and lower plate 202 remain in the vacuum pressure that forces down than atmosphere.Between upper plate 201 and lower plate 202, be provided with dividing plate 192, be used to support upper plate 201 and lower plate 202 and limit emission space 210.
Apply at anode 180 and to be used to quicken from the required high pressure of electron emission source 160 electrons emitted, make electronics can with fluorescence coating 170 high velocity impacts.The fluorescent material of fluorescence coating 170 sends visible light when being subjected to electron excitation, transit to low-lying level from high level this moment.
Gate electrode 140 is used to make electronics easily from electron emission source 160 emissions.Insulating barrier 130 limits electronics launch hole 169, is used for electron emission source 160 and gate electrode 140 insulation.
Although shown electron emission device herein with audion shown in Figure 1, have the electron emission device of diode structure except audion etc., also fall within the scope of the invention.And, the present invention also can be applied to gate electrode wherein and be arranged in the electron emission device on the negative electrode lower surface, and be applied in the electron emission device with grid/network, described grid/network is damaged and focused electron emission source electrons emitted by electric arc (supposition is produced by electric discharge phenomena) in order to prevent gate electrode and/or negative electrode.Certainly, the structure of above-mentioned electron emission device also can be applied in the display device.
Below, will the present invention more specifically be described by embodiment.But the following examples only are used for example, and the present invention is not limited to these embodiment or is limited by these embodiment.
In the 10g terpinol, add 1g CNT powder (MWNT, Iljin Nanotech, Korea), 10g Al
2O
3(particle diameter: 500nm), 5g polyester acrylate and 5g benzophenone, stir, preparation forms the composition of electron emission source.
According to preparing the composition that forms electron emission source, except using TiO with preparation embodiment 1 identical mode
2Replace Al
2O
3
According to preparing the composition that forms electron emission source, except using SnO-P with preparation embodiment 1 identical mode
2O
5Replace 10g Al
2O
3
According to preparing the composition that forms electron emission source, except replacing Al as containing the Pb frit with PbO with preparation embodiment 1 identical mode
2O
3
Adopt every kind of preparation of compositions sample of 1g preparation in preparation embodiment 1-3 and comparative preparation embodiment 1.Each sample in nitrogen atmosphere in 450 ℃ of first sintering 5 hours, then in air atmosphere in 450 ℃ of double sinterings.Measure first sintering and double sintering electron emission amount afterwards.Following table 1 has been listed the poor of behind first sintering and double sintering electron emission amount, with residual volume (%) expression.
Table 1
| Sample | Electron emission amount (μ A/cm 2@5V/μm) | ||
| First sintering | Double sintering | Residual volume (%) | |
| | 500 | 493 | 98.6 |
| | 389 | 422 | 108 |
| | 808 | 331 | 41 |
| | 416 | 0 | 0 |
As shown in the table 1, consider comparative preparation embodiment 1, the electron emission amount behind double sintering significantly reduces.On the contrary, consider preparation embodiment 1-3, even the maintenance of electron emission amount is also satisfactory behind double sintering.
In order to determine to add the Al that is used to prepare the composition that forms electron emission source
2O
3With the influence of no Pb frit, carried out following test.
To three kinds of samples, that is, and CNT, CNT and Al
2O
3Mixture and Al
2O
3, carrying out differential thermal analysis (DTA), analysis result is as shown in Figure 2.
To three kinds of samples, that is, CNT, CNT and do not have the mixture of Pb frit and do not have the Pb frit carry out DTA, and analysis result as shown in Figure 3.
To three kinds of samples, that is, mixture and PbO that CNT, CNT and conduct contain the PbO of Pb frit carry out DTA, and analysis result as shown in Figure 4.
Referring to Fig. 4, compare with the DTA of CNT, the DTA that contains the Pb frit that promotes CNT to degenerate exothermic peak occurred at lower temperature.Referring to Fig. 2 and 3, compare Al with the DTA of CNT
2O
3In higher temperatures exothermic peak has appearred with the DTA of no Pb frit.Can find Al from these DTA results
2O
3Effectively prevented the degeneration of CNT with no Pb frit.
The composition for preparing the formation electron emission source of embodiment 1 preparation is printed on the electron emission source zone of substrate, comprises Cr gate electrode, insulating barrier and ITO electrode on this substrate.Adopt pattern mask then and the equipment 2000mJ/cm that similarly exposes
2Exposure energy expose.The structure of exposure back gained is developed with acetone, and the mist of oxygen and nitrogen (oxygen concentration: about 1000ppm) in 450 ℃ of sintering, thereby the formation electron emission source.
Then, the substrate of the anode that includes fluorescence coating on it and made by ITO is set, the substrate that includes electron emission source on itself and its is faced one another, between these two substrates, form dividing plate then, between these two substrates, keep cell gap, thereby finish electron emission device.
Adopt the composition of the formation electron emission sources of preparation embodiment 2 and 3 preparations to substitute the composition of the formation electron emission source of preparation in preparation embodiment 1, according to the mode identical, preparation electron emission device with embodiment 1.
The comparative example 1
Adopt the composition of the formation electron emission source of comparative preparation embodiment 1 preparation to substitute the composition of the formation electron emission source of preparation in preparation embodiment 1, according to the mode identical, preparation electron emission device with embodiment 1.
Adopt the pulse power and ammeter to measure the current density of the electron emission device of preparation in embodiment 1-3 and comparative example 1.
According to the measurement result of current density, to compare with comparative example 1 electron emission device, the electron emission device of embodiment 1-3 demonstrates the current density characteristic and is improved, and electron emission characteristic is improved then.
According to the composition of formation electron emission source of the present invention can be in the forming process of electron emission source in air atmosphere sintering.So the CNT in the time of can significantly reducing carbon laydown behind the sintering and sintering degenerates, thereby has formed the electron emission source with high current density, these are different with conventional electrical emission source formation method.Use the electron emission source that forms thus to make and to prepare the electron emission device that reliability is improved.
Claims (25)
1. electron emission source comprises:
Carbon-based material; With
At least a Al that is selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm.
2. the electron emission source of claim 1, wherein, based on the carbon-based material of 1 weight portion, the content of described metal oxide is the 5-100 weight portion.
3. the electron emission source of claim 1 also comprises unleaded (Pb) frit of 0.25-10 weight portion, based on the carbon-based material of 1 weight portion.
4. the electron emission source of claim 3, wherein said no Pb frit is tin oxide-phosphorus pentoxide (SnO-P
2O
5).
5. electron emission source comprises:
Carbon-based material; With
No Pb frit.
6. the electron emission source of claim 5, wherein said no Pb frit is SnO-P
2O
5
7. the electron emission source of claim 5, wherein, based on the carbon-based material of 1 weight portion, the content of described no Pb frit is the 0.25-10 weight portion.
8. electron emission device comprises:
First substrate of being arranged to face one another and second substrate;
The negative electrode that on described first substrate, forms;
With the electron emission source that the described cathodic electricity that forms on described first substrate is connected, it comprises carbon-based material and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm;
The anode that on described second substrate, forms; With
Fluorescence coating, it causes luminous by described electron emission source electrons emitted.
9. electron emission device comprises:
First substrate of being arranged to face one another and second substrate;
The negative electrode that on described first substrate, forms;
With the electron emission source that the described cathodic electricity that forms on described first substrate is connected, it comprises carbon-based material and at least a Al of being selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm, wherein based on the carbon-based material of 1 weight portion, the content of described metal oxide is the 5-100 weight portion;
The anode that on described second substrate, forms; With
Fluorescence coating, it causes luminous by described electron emission source electrons emitted.
10. electron emission device comprises:
First substrate of being arranged to face one another and second substrate;
The negative electrode that on described first substrate, forms;
With the electron emission source that the described cathodic electricity that forms on described first substrate is connected, it comprises carbon-based material and no Pb frit;
The anode that on described second substrate, forms; With
Fluorescence coating, it causes luminous by described electron emission source electrons emitted.
11. an electron emission device comprises:
First substrate of being arranged to face one another and second substrate;
The negative electrode that on described first substrate, forms;
With the electron emission source that the described cathodic electricity that forms on described first substrate is connected, it comprises carbon-based material and no Pb frit, and wherein based on the carbon-based material of 1 weight portion, the content of described no Pb frit is the 0.25-10 weight portion;
The anode that on described second substrate, forms; With
Fluorescence coating, it causes luminous by described electron emission source electrons emitted.
12. a composition that forms electron emission source comprises:
Carbon-based material;
The carrier that constitutes by resin Composition and solvent composition; With
At least a Al that is selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm.
13. the composition of claim 12, wherein, based on the carbon-based material of 1 weight portion, the content of described metal oxide is the 5-100 weight portion.
14. the composition of claim 12, the particle diameter of wherein said metal oxide makes that through adjusting the difference of particle diameter (D90) of the particle diameter (D10) of 10 weight % particle size distribution and 90% particle size distribution is 300nm or littler.
15. the composition of claim 12 also comprises the no Pb frit of 0.25-10 weight portion, based on the carbon-based material of 1 weight portion.
16. the composition of claim 15, wherein said no Pb frit is SnO-P
2O
5
17. a composition that forms electron emission source comprises:
Carbon-based material;
The carrier that constitutes by resin Composition and solvent composition; With
No Pb frit.
18. the composition of claim 17, wherein said no Pb frit is SnO-P
2O
5
19. the electron emission source of claim 17, wherein, based on the carbon-based material of 1 weight portion, the content of described no Pb frit is the 0.25-10 weight portion.
20. a method that forms electron emission source, described method comprises:
Preparation forms the composition of described electron emission source, and it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With at least a Al that is selected from
2O
3, TiO
2And SiO
2, average particulate diameter is the metal oxide of 100-1000nm;
The composition of described formation electron emission source is printed on the substrate; With
In oxygen atmosphere or contain the described printed compositions of sintering in the atmosphere of mist of oxygen and nitrogen.
21. a method that forms electron emission source, described method comprises:
Preparation forms the composition of described electron emission source, and it comprises: carbon-based material; The carrier that constitutes by resin Composition and solvent composition; With no Pb frit;
The composition of described formation electron emission source is printed on the substrate; With
In oxygen atmosphere or contain the described printed compositions of sintering in the atmosphere of mist of oxygen and nitrogen.
22. the method for claim 20, the composition of wherein said formation electron emission source also comprise at least a component that is selected from photoresist resin, light trigger and filler; With
The composition that wherein prints described formation electron emission source comprises:
Composition with described formation electron emission source applies described substrate; With
Exposure of electron emission source area and development according to described substrate.
23. the method for claim 21, the composition of wherein said formation electron emission source also comprise at least a component that is selected from photoresist resin, light trigger and filler; With
The composition that wherein prints described formation electron emission source comprises:
Composition with described formation electron emission source applies described substrate; With
Exposure of electron emission source area and development according to described substrate.
24. the method for claim 20, wherein the described printed compositions of sintering is carried out 350-500 ℃ temperature.
25. the method for claim 21, wherein the described printed compositions of sintering is carried out 350-500 ℃ temperature.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2005-0017180 | 2005-03-02 | ||
| KR1020050017180A KR101082437B1 (en) | 2005-03-02 | 2005-03-02 | An electron emission source, a preparing method thereof, and an electron emission device using the same |
| KR1020050017180 | 2005-03-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1828802A true CN1828802A (en) | 2006-09-06 |
| CN1828802B CN1828802B (en) | 2011-01-05 |
Family
ID=36370971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100588998A Expired - Fee Related CN1828802B (en) | 2005-03-02 | 2006-03-02 | Electron emission source, its method of fabrication, an electron emission device using the electron emission source |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7960903B2 (en) |
| EP (1) | EP1699068B1 (en) |
| JP (1) | JP4461106B2 (en) |
| KR (1) | KR101082437B1 (en) |
| CN (1) | CN1828802B (en) |
| DE (1) | DE602006020204D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102124536A (en) * | 2008-08-22 | 2011-07-13 | E.I.内穆尔杜邦公司 | Method of making air-fired cathode assemblies in field emission devices |
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| KR20070105491A (en) * | 2006-04-26 | 2007-10-31 | 삼성에스디아이 주식회사 | A composition for preparing an electron emitter, the electron emitter prepared using the composition, and backlight unit having the emitter |
| US7798882B2 (en) * | 2006-08-09 | 2010-09-21 | Samsung Sdi Co., Ltd. | Method of manufacturing electron emission device and electron emission device manufactured by the method |
| KR20080047917A (en) * | 2006-11-27 | 2008-05-30 | 삼성에스디아이 주식회사 | A carbon-based material for an electron emission source, an electron emission source comprising the same, an electron emission device comprising the electron emission source and a method for preparing the electron emission source |
| KR100777113B1 (en) | 2006-12-07 | 2007-11-19 | 한국전자통신연구원 | The fine patternable cnt emitter manufacturing method of with high reliability |
| KR20090044797A (en) * | 2007-11-01 | 2009-05-07 | 삼성에스디아이 주식회사 | Boron nitride nano tube paste composition, electron emission source using thereof, electron emission device employing the electron emission source, and backlight unit and electron emission display device employing the electron emission device |
| KR102397196B1 (en) * | 2019-12-30 | 2022-05-12 | 고려대학교 산학협력단 | Carbon nanotube (cnt) paste emitter, method for manufacturing the same and x-ray tube using the same |
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| US6565403B1 (en) * | 1997-12-15 | 2003-05-20 | E. I. Du Pont De Nemours And Company | Ion-bombarded graphite electron emitters |
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| JP5060722B2 (en) * | 2004-11-10 | 2012-10-31 | 日立粉末冶金株式会社 | Composition for forming electron emission source and method for forming coating film for electron emission source |
| KR20060117823A (en) * | 2005-05-14 | 2006-11-17 | 삼성에스디아이 주식회사 | An electron emission source, a preparing method thereof, and an electron emission device using the same |
-
2005
- 2005-03-02 KR KR1020050017180A patent/KR101082437B1/en not_active IP Right Cessation
-
2006
- 2006-02-14 JP JP2006037160A patent/JP4461106B2/en not_active Expired - Fee Related
- 2006-02-27 US US11/362,210 patent/US7960903B2/en not_active Expired - Fee Related
- 2006-03-01 EP EP06110540A patent/EP1699068B1/en not_active Expired - Fee Related
- 2006-03-01 DE DE602006020204T patent/DE602006020204D1/en active Active
- 2006-03-02 CN CN2006100588998A patent/CN1828802B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102124536A (en) * | 2008-08-22 | 2011-07-13 | E.I.内穆尔杜邦公司 | Method of making air-fired cathode assemblies in field emission devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006244995A (en) | 2006-09-14 |
| DE602006020204D1 (en) | 2011-04-07 |
| US7960903B2 (en) | 2011-06-14 |
| EP1699068A2 (en) | 2006-09-06 |
| US20060197429A1 (en) | 2006-09-07 |
| KR101082437B1 (en) | 2011-11-11 |
| JP4461106B2 (en) | 2010-05-12 |
| EP1699068A3 (en) | 2006-10-04 |
| KR20060096561A (en) | 2006-09-13 |
| CN1828802B (en) | 2011-01-05 |
| EP1699068B1 (en) | 2011-02-23 |
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